Azo dye



Patented July 4, 1939 2,164,524

AZO DYE Henry Jordan and Swanie S. Rossander, Wilmington, Del.,assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., acorporation of Delaware No Drawing. Application July 3, 1937, Serial No.151,961

6 Claims. (Cl. 260-169) a A. This invention relates to direct azo dyesfor acetate. Heat slowly to 40 C. Stir the coucellulose, within whichterm is included those pling overnight. Add 30% sodium chloride.compounds commonly referred to as cellulose and Stir four hours. Filteracid to litmus. Dissolve regenerated cellulose. Y the residue in 250parts of water and 6.3 parts 10 B. Thereis a demand in the tradefor'develnormal sodium hydroxide (alkaline to Brilliant oped reddish andbrown shades of cellulose dyes Yellow paper). Adjust the temperature to22- which have exceptional fastness to washing and. 24 C. Add 13 partsof normal hydrochloric excellent discharge properties. In order to meetacid and 23.5 parts of 2 normal sodium nitrite this demand, it has beennecessary not only to solution. Hold a definite excess of sodium 10create new dyestuffs but new intermediates. nitrite for one hour. Removeany trace of excess 10 We have discovered that the dyes of the presentsodium nitrite with urea. invention are useful not only for the directcolor- Dissolve 6.42 parts of meta toluidine in 50 parts ing ofcellulose but are also useful when develof water and 6 parts of 10normal hydrochloric oped on the fiber with suitable coupling comacid.Add to the above diazo. Make neutral to ponents in the production ofcolors of the indi- Congo by the addition of 12 parts of sodium 15 catedshades and with the required properties. acetate. Stir the couplingovernight. Add C. It is an object of this invention to prepare sodiumchloride. Heat to 70 C. Make acid to dyestufis which are applicable asdirect dyes to Congo by adding hydrochloric acid and filter. cellulose.There has been an increasing demand Dissolve the residue in 500 parts ofwater and 6 20 in the art for dyestufis of direct reddish shade parts of10 normal sodium hydroxide and 20 parts which are easily applied and arehighly subof 2 normal sodium carbonate. (Alkaline to Brilstantive' tothe fiber and which show high fastliant Yellow paper.) Heat to 90 C. Add10 ness properties. Y Y Y Y parts nuchar and 5 parts filter-eel. Hold at90 D. The objects of the invention are accom 'C. for ten minutes andfilter. Add 20% sodium plished'by the manufacture and use of aninterchloride to the filtrate, stir one-half hour and 25 mediate being atrisazo dye having 2-amino-benfilter. zidine as an end component. Thedyestuffs of Dissolve the residue in 500 parts of water. Cool 1 thisinvention are made water-soluble by having to 25-30 C. Add 13 parts of10 normal hydroa water-sol iliz n p, h as lf nic or chloric acid and 20parts of 2 normal sodium so carboxy ic a id in a ea o e of t e nd u einitrite solution. Hold a definite end point of of the Y i Y Y Y excesssodiumnitrite for one hour. Remove any fonPwmg examples lnustra'te butdo trace of excess sodium nitrite with urea.

not hmlt the mventmn: Dissolve 15.4 parts Z-amino-benzidine as theExample I tri-hydrochloride in 50 parts of Water. Add to Dissolve 15.1parts of Z-naphthylamine-GtS-dithe diam Make the neutral t0 sulfonicacid in 100 parts oi water. 0001 to 10 cqngo e 50 Pall/S 2 normal Sodiume o. Add 12.5 parts of 10 normal hydrochloric Sill" overmght- Heat to -imake acld to acid, foll wed by 25 parts of 2 normal sodium Congo withhydrochloric acidand filter. Paste 40 t t m one-half hour end point it athe-residue with 6 parts of dry sodium carbonate 4 slight excess ofsodium nitrite at 10 15 C. and dry. The product is a dark powder whichDissolve 6.7 parts of meta toluidine in 50 parts is soluble in water.The probable formula of the of water and 6.3 parts-"10 normal,hydrochloric dye is;

acid. Add to the above diazo. Make neutral to Y Y N112 Y Congo by theaddition of 20 parts of sodium 45 1 Neois 311. our NH, 50

. Nao Y NH, 5

Color of Composition of product dyeing 2-naphthylamine-6:8-disulfouicacid)meta-toluidine-)meta-toluidine- 2-amino-benzidine.

2-naphthylamine-4z8-disulfonic acid mets-t0luidine meta-toluidine-2-amino-benzidine.

Violet.

Black.

G. The aryl groups of the components may have substituents other thanthose specifically mentioned. These substituents are halogen, alkyl,alkoxy, carboxy, and sulfonic acid. The aryl components, other than2-amino-benzidine, are preferably of the benzene or naphthalene series,but may be of other series, for instance, diphenyl. The end component,other than Z-amino-benzidine, may also consist of a component having asingle phenyl-alkyl-pyrazolone nucleus. In making the dyes it must beobserved that the middle coupling components be of such composition thatthe coupling product is capable of diazotization and further coupling.Meta-toluidine, alphanaphthylamine, 1 naphthylamine 6 sulionic acid, andZ-amino-S-naphthol-T-sulfonic acid are examples of components which areparticularly suited for middle components.

H. Adequate solubility is usually assured by having twowater-solubilizing groups attached to the nucleus.

NaOaS production of direct reds to browns when de-' veloped on thefiber.

K. As many apparently widely difierent embodiments of this invention maybe made without departing from the spirit and scope thereof, it is to beunderstood that we do not limit ourselves to the specific embodimentsthereof except as defined in the appended claims.

We claim:

1. A water-soluble compound represented by the formula:

in which Y is one or more of the group consisting of hydrogen, halogen,alkyl, alkoxy, carboxy, and sulfonic acid, at least one Y being awatersolubilizing group and the end aryl has a single nucleus from theclass consisting of benzene, naphthalene, diphenyl,phenyl-methylpyrazolone, and aryl of interior components has a singlenucleus from the class consisting of. benzene, naphthalene, anddiphenyl.

2. A compound represented in the form of its sodium salt by the formula:

( 3H: OH: NH:

S OaNa I. In addition to their use as direct dyes these compounds arealso useful for the production of NaOaS 1 Naoasm dyes on the fiber, andfor conversion to aminoaroyl derivatives which are useful in dyeingcotton and regenerated cellulose. It is to be noted that the dyes excelin substantivity to cellulose.

J. These colors have outstanding washing fastness and excellentdischarge properties. They themselves vary from bright orange to violetin color on cellulose, but are remarkable for the 3. A compoundrepresented in the form of its A sodium salt by the formula:

red, stirring and heating, filtering,.dissolving and purifying,diazotizing, and adding an aqueous medium containing2-amino-benzidine-trihydrochloride, neutralizing to Congo red, heating,agitating, and isolating the product.

5. The process which comprises diazotizing 2-naphthylamine-6:8-disulfonic acid, coupling it to meta-toluidine,diazotizing the product, and coupling it to meta-toluidine, diazotizingthe product and. coupling it to 2-amino-benzidine.

6. Theprocess which comprises diazotizing the compound represented bythe formula in which Y is one of a group consisting of hy drogen,halogen, alkyl, alkoxy, carboxy, and sulfonic acid, coupling it to adiazotizable primaryarylamine containing Y as defined, at least one Ybeing a water-solubilizing group, diazotizing the resulting compound,and coupling it to 2- amino-benzidine.

HENRY JORDAN. SWANIE S. ROSSANDER.

